CN105664951A - Copper nickel-zinc oxide composite nanocrystalline photocatalyst and preparation method and application thereof - Google Patents
Copper nickel-zinc oxide composite nanocrystalline photocatalyst and preparation method and application thereof Download PDFInfo
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- CN105664951A CN105664951A CN201610090884.3A CN201610090884A CN105664951A CN 105664951 A CN105664951 A CN 105664951A CN 201610090884 A CN201610090884 A CN 201610090884A CN 105664951 A CN105664951 A CN 105664951A
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- zinc oxide
- alkylamine
- photocatalyst
- copper
- nickel
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RNLGOFZPXVIQCG-UHFFFAOYSA-N [O--].[O--].[O--].[Ni++].[Cu++].[Zn++] Chemical compound [O--].[O--].[O--].[Ni++].[Cu++].[Zn++] RNLGOFZPXVIQCG-UHFFFAOYSA-N 0.000 title abstract 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000243 solution Substances 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000011787 zinc oxide Substances 0.000 claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- -1 copper nickel-zinc oxide compound Chemical class 0.000 claims description 28
- 238000009413 insulation Methods 0.000 claims description 25
- 150000001412 amines Chemical class 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 11
- 229940043267 rhodamine b Drugs 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 9
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 9
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 8
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 7
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- 229960004217 benzyl alcohol Drugs 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 238000002835 absorbance Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000000407 epitaxy Methods 0.000 claims description 2
- SRYDOKOCKWANAE-UHFFFAOYSA-N hexadecane-1,1-diol Chemical compound CCCCCCCCCCCCCCCC(O)O SRYDOKOCKWANAE-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 230000005540 biological transmission Effects 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000012452 mother liquor Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000003252 repetitive effect Effects 0.000 description 8
- 238000005201 scrubbing Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 4
- 229960003280 cupric chloride Drugs 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 229910052984 zinc sulfide Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001534 heteroepitaxy Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention provides a copper nickel-zinc oxide composite nanocrystalline photocatalyst and a preparation method and application thereof, and relates to a nanometer photocatalyst. Duplex metal of copper and nickel serves as a kernel of the copper nickel-zinc oxide composite nanocrystalline photocatalyst, the core is completely or partially coated with zinc oxide nanocrystalline, a stable heterogeneous interface is formed through epitaxial growth, and the composite nanocrystalline is formed. The preparation method comprises the steps that a metal precursor, alkylamine or a mixed solution of alkylamine and organic solvent and a surfactant are added into a reaction vessel, the materials are mixed and reacted, and a reaction solution A is obtained; a zinc oxide precursor and alkylamine or the mixed solution of alkylamine with the organic solvent are added into another vessel, the materials are heated and reacted, and a reaction solution B is obtained; the reaction solution B is injected into the reaction solution A, the temperature is raised to 190-300 DEG C, heat preservation is conducted for 10-120 min, the solution is cooled to room temperature, a product is washed with an organic solvent mixed solution, centrifugal separation and vacuum drying are conducted, and a product is obtained. The photocatalyst can be applied to preparation of a photocatalytic degradation agent of organic dye.
Description
Technical field
The present invention relates to nano-photocatalyst, especially relate to the brilliant photocatalyst of a kind of copper nickel-zinc oxide compound nano and its preparation method and application.
Background technology
Along with the development of human society, problem of environmental pollution seems day by day outstanding, and causes popular extensive concern. In the middle of various environmental pollution, the most generally, main and to affect maximum be chemical pollution. Wherein, the toxic and harmful substance in organic waste water is particularly serious to the pollution of water quality. Therefore, effectively controlling and administer various chemical pollutant to the destruction of water resources is the emphasis in comprehensive environmental improvement. At present the main water treatment method used has microbiological treatment, physisorphtion, chemical oxidization method and photodissociation hydrolysis etc., these methods also exist that cost is higher or processing efficiency is lower to some extent, can not thoroughly degradation of contaminant, easily cause the deficiency of the aspects such as secondary pollution, only applicable specific pollutent. In this case, photocatalysis technology develops fast because its less energy-consumption, high-level efficiency, use range are wide and have deep oxidation ability to obtain in process organic waste water. Zinc oxide is a kind of wide bandgap semiconductor photocatalyst material, and its energy gap is about 3.2eV, under UV-irradiation, can produce photic electron-hole pair, have good photocatalysis performance, and organic pollutant can be degraded into H completely2O、CO2And mineral ion, non-secondary pollution. Meanwhile, photocatalyst of zinc oxide self is nontoxic, therefore can repeat to recycle. But, owing to compound easily occurs under to a certain degree in the photic electronics-hole of zinc oxide, this will reduce photocatalysis efficiency. Wherein a kind of terms of settlement be by metal group unit with zinc oxide in nanoscale compound, form the metal-oxide zinc composite nanocrystalline of a fixed structure, the Schottky barrier now formed after zinc oxide and metal composite can effectively suppress the compound of photo-generated carrier, promote the separation in electronics-hole, thus effectively improve the photocatalysis efficiency of zinc oxide, there is important using value in fields such as photochemical catalysis.
But, owing to the lattice mismatch degree of common transition metal and zinc oxide is relatively big, thus it is difficult to realize at nanoscale the extension compound of heterojunction structure with zinc oxide.Existing report is brilliant about precious metal-zinc oxide compound nano mostly, and owing to the cost of precious metal (Au, Ag, Pt etc.) is higher, preparation process energy consumption height, the photocatalyst prepared with it is unfavorable for large-scale commercial applications. Meanwhile, about the report of base metal-composite nanocrystalline be mostly by base metal nanoparticulate dispersed on zinc oxide carrier, owing to combining by means of only more weak physical adsorption between each group of unit, it is unfavorable for the transmission of current carrier, also easily cause coming off of metallic particles simultaneously, greatly reduce photocatalysis efficiency. (Nanoscale, 2014,6 such as Flomin, 1335-1339) reporting the Cu-ZnO nanostructure of pyramid shape, but its copper particle is attached to zinc oxide surface and is easy to oxidation, shape looks are single, and particle easily reunites, output is lower, does not also possess the controlled recyclability of magnetic. Up to now, there is not yet the successful preparation report being formed the brilliant photocatalyst of copper nickel-zinc oxide compound nano by stable interface bond.
Summary of the invention
It is an object of the invention to for the brilliant more high deficiency of photocatalyst raw materials cost of existing precious metal-zinc oxide compound nano, it is intended to substitute precious metal with cheap copper nickel, it is provided that the brilliant photocatalyst of a kind of copper nickel-zinc oxide compound nano and its preparation method and application.
The brilliant photocatalyst of described copper nickel-zinc oxide compound nano take cuprum nickle duplex metal as core, coating zinc oxide nanometer crystalline substance wholly or in part outside core, stable heterogeneous interface is formed by epitaxy, and form composite nanocrystalline, described composite nanocrystalline comprises branched rack-like composite nanocrystalline, the nano wire of nucleocapsid structure, the nano particle of nucleocapsid structure, pyramid shape composite nanocrystalline etc., described composite nanocrystalline is of a size of 20～400nm, core is of a size of 10～200nm, the mol ratio of nickel in core can be 0～40%, and the mol ratio of nickel in core is not 0.
The preparation method of the brilliant photocatalyst of described copper nickel-zinc oxide compound nano, comprises the following steps:
1) under the protection of rare gas element, metal precursor, alkylamine or alkylamine and organic solvent mixed solution, tensio-active agent are added hybrid reaction in reaction vessel, obtains reaction solution A; Described metal precursor comprises copper metal precursor and nickel metal precursor;
2) in another container, zinc oxide precursor, alkylamine or alkylamine and organic solvent mixed solution is added; mix under the protection of rare gas element; reaction solution B is obtained after reacting by heating; reaction solution B is injected into step 1) in the reaction solution A of gained; it is warming up to 190～300 DEG C again; insulation 10～120min; then room temperature it is cooled to; product organic solvent mixed solution cleans; centrifugation again; after vacuum-drying, obtaining the brilliant photocatalyst of copper nickel-zinc oxide compound nano, the brilliant photocatalyst of gained copper nickel-zinc oxide compound nano is powder body.
In step 1) in, described copper metal precursor can be selected from acetylacetonate compound or the halide salt of copper; Described nickel metal precursor can be selected from the acetylacetonate compound of nickel; The molar percentage of described copper metal precursor in metal precursor can be 60%～100%; Described alkylamine can be selected from oil amine or stearylamine etc.; Described organic solvent can be selected from dibenzyl ether or phenylcarbinol etc.; The molar percentage of described alkylamine in alkylamine and organic solvent mixed solution can be 20%～100%; Described tensio-active agent agent can be selected from cetyl alcohol, dodecane glycol, hexadecane diol, three octyl group phosphorus oxide etc. one or both;The mol ratio of described metal precursor, alkylamine or alkylamine and organic solvent mixed solution can be 0.01～0.2; The mol ratio of described metal precursor and tensio-active agent can be 1～8; The temperature of described reaction can be 180～280 DEG C, and the time of reaction can be 10～60min.
In step 2) in, described zinc oxide precursor can be selected from the one in zinc acetate, Zinic stearas etc.; Described zinc oxide precursor and step 1) in the mol ratio of metal precursor can be 1～15; The one that described alkylamine can be selected from oil amine, cetylamine, trioctylamine etc.; Described organic solvent can be selected from phenylcarbinol or dibenzyl ether etc., and described alkylamine molar percentage in alkylamine and organic solvent mixed solution can be 40%～100%; The consumption of described alkylamine or alkylamine and organic solvent mixed solution and step 1) in alkylamine or the volume ratio of alkylamine and organic solvent mixed solution consumption can be 0.1～1; The temperature of described reacting by heating can be 60～80 DEG C, and the time of reacting by heating can be 5～30min; Described injection can adopt syringe abstraction reaction liquid B, is injected into step 1 by syringe pump or manual mode) in the reaction solution A of gained; The time of described injection can be 10～40s; 2～6 times capable of washing of described cleaning.
The brilliant photocatalyst of described copper nickel-zinc oxide compound nano can prepare application in organic dye photocatalytic degradation agent. The concrete steps of described application are as follows:
Brilliant for copper nickel obtained by 10mg-zinc oxide compound nano photocatalyst is positioned in the aqueous solution of rhodamine B organic dye that 100mL concentration is 10mg/L, darkroom is stirred 2h, to reach adsorption equilibrium; Then start to carry out photocatalytic with the ultraviolet lamp of 175W, just take out the solution after a certain amount of light-catalyzed reaction at set intervals; When rhodamine B degraded becomes colorless completely, just stop the irradiation of ultraviolet lamp; The rhodamine B solution centrifugal of different palliating degradation degrees that will take out again, then carries out absorption spectrum test, calculate its at set intervals after the absorbancy of rhodamine B and the ratio C/C of initial absorbance0(degradation curve).
The brilliant photocatalyst of copper nickel prepared by the present invention-zinc oxide compound nano has catalytic efficiency height, morphology controllable, good dispersity, the advantage such as with low cost compared with the photocatalyst containing precious metal; Secondly, this catalyzer also has magnetic controllability, and what be conducive to catalyzer repeats recycling; Again, due to the introducing of nickel, can greatly improve the resistance of oxidation of copper and the practicality of catalyzer; Finally, the metal core shape looks of catalyzer and size can by regulating various reaction parameter to be controlled, and the shape looks of outer oxide zinc and size also can conveniently be regulated and controled, to be adapted to different application scenarios. The preparation method of this catalyzer has the advantages such as preparation flow is simple, with low cost, the reaction times is short. Particularly the method can be realized cuprum nickle duplex metal and is combined with semiconductor oxide zinc by hetero epitaxy, and this is showed no document report at home and abroad, overcomes existing method and need to use the deficiency that expensive precious metal could realize hetero epitaxy.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the copper-zine oxide composite nanocrystalline prepared by embodiment 1, and scale is 0.2 μm.
Fig. 2 is the X-ray diffractogram of the copper-zine oxide composite nanocrystalline prepared by embodiment 1, and X-coordinate is diffraction angle 2 θ (degree), and ordinate zou is intensity (a.u.).
Fig. 3 is the transmission electron microscope photo of the copper-zine oxide composite nanocrystalline prepared by embodiment 2, and scale is 50nm.
Fig. 4 is the X-ray diffractogram of the copper-zine oxide composite nanocrystalline prepared by embodiment 2, and X-coordinate is diffraction angle 2 θ (degree), and ordinate zou is intensity (a.u.).
Fig. 5 is the transmission electron microscope photo of the copper-zine oxide composite nanocrystalline prepared by embodiment 3, and scale is 200nm.
Fig. 6 is the X-ray diffractogram of the copper-zine oxide composite nanocrystalline prepared by embodiment 3, and X-coordinate is diffraction angle 2 θ (degree), and ordinate zou is intensity (a.u.).
Fig. 7 is the transmission electron microscope photo of the copper-zine oxide composite nanocrystalline prepared by embodiment 4, and scale is 0.2 μm.
Fig. 8 is the X-ray diffractogram of the copper-zine oxide composite nanocrystalline prepared by embodiment 4, and X-coordinate is diffraction angle 2 θ (degree), and ordinate zou is intensity (a.u.).
Fig. 9 is the transmission electron microscope photo of the nickel of the copper prepared by embodiment 5-zinc oxide compound nano crystalline substance, and scale is 100nm.
Figure 10 is the energy spectrogram of the brilliant metal core of the nickel of the copper prepared by embodiment 5-zinc oxide compound nano, and X-coordinate is energy (keV), and ordinate zou is counting rate. It may be seen that the peak of copper and mickel is very strong.
Figure 11 is the transmission electron microscope photo of the nickel of the copper prepared by embodiment 6-zinc oxide compound nano crystalline substance, and scale is 100nm.
Figure 12 is the energy spectrogram of the scanning transmission line sweep of the nickel of the copper prepared by embodiment 6-zinc oxide compound nano crystalline substance, and X-coordinate is position (nm), and ordinate zou is counting rate. Confirming that the metal core of this product is made up of copper and mickel, being coated on outer field is zinc oxide.
Figure 13 is the transmission electron microscope photo of the nickel of the copper prepared by embodiment 7-zinc oxide compound nano crystalline substance, and scale is 100nm.
Figure 14 is the transmission electron microscope photo of the nickel of the copper prepared by embodiment 8-zinc oxide compound nano crystalline substance, and scale is 0.2 μm.
Figure 15 is the curve of the brilliant photocatalytic degradation rhodamine B with pure zinc oxide of the nickel of the copper prepared by embodiment 7-zinc oxide compound nano. X-coordinate is time (min), ordinate zou be at set intervals after the absorbancy of rhodamine B and the ratio C/C of initial absorbance0. In figure, curve a is for adding pure zinc oxide nanocrystalline catalyst, and curve b is the brilliant photocatalyst of copper nickel-zinc oxide compound nano adding embodiment 7. It may be seen that the photocatalysis efficiency of zinc oxide compound nano crystalline substance is better than single zinc oxide nanocrystalline.
Figure 16 is the photo that the nickel of the copper prepared by embodiment 7-zinc oxide compound nano crystalline substance is separated from mother liquor by magnet adsorption.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1:
0.2mmol acetylacetone copper, 1.5mmol tri-octyl group phosphorus oxide, 4ml oil amine, 4ml phenylcarbinol are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 200 DEG C, insulation 40min. In addition; 0.15g zinc acetate and 2ml oil amine are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 80 DEG C of about 20min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 40min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 30s at once. After having injected, then it is warming up to 190 DEG C, insulation 60min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Fig. 1 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of the oxide coated by zinc copper metal core of branched frame, and the size of metal core is on average about 40nm.Fig. 2 is X-ray diffraction (XRD) figure of this product, it was demonstrated that product is the copper of face-centred cubic structure, and the zinc oxide of wurtzite structure.
Embodiment 2:
0.15mmol acetylacetone copper, 0.5mmol tri-octyl group phosphorus oxide and 7ml oil amine are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 200 DEG C, insulation 30min. In addition; by 0.35g Zinic stearas; 2ml oil amine adds in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 80 DEG C of about 10min, then this mixing solutions is drawn with syringe clean, after the reaction solution in four-hole bottle is just incubated 30min; being expelled in the reaction solution in four-hole bottle, whole injection process is about 20s at once. After having injected, then it is warming up to 285 DEG C, insulation 40min. Reaction solution naturally cools to room temperature, adds acetone and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Fig. 3 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of the coated copper metal core of multiple zinc oxide pyramid. Fig. 4 is X-ray diffraction (XRD) figure of this product, it was demonstrated that product is the copper of face-centred cubic structure and the zinc oxide of wurtzite structure.
Embodiment 3:
0.2mmol acetylacetone copper, 0.3g dodecane glycol, 0.8mmol tri-octyl group phosphorus oxide, 2ml oil amine, 3ml bis-Bian ether are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 200 DEG C, insulation 25min. In addition; 0.15g zinc acetate, 1ml oil amine, 1.5ml bis-Bian ether are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 75 DEG C of about 15min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 25min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 40s at once. After having injected, then it is warming up to 265 DEG C, insulation 30min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Fig. 5 is the transmission electron microscope photo of this product, and product is the nucleocapsid composite nanocrystalline of the coated copper metal core of zinc oxide shell, and the size of metal core is on average about 60nm. Fig. 6 is X-ray diffraction (XRD) figure of this product, it was demonstrated that product is the copper of face-centred cubic structure, and the zinc oxide of wurtzite structure.
Embodiment 4:
0.2mmol cupric chloride, 0.2mmol tri-octyl group phosphorus oxide, 7.5ml oil amine are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 220 DEG C, insulation 50min. In addition; 0.45g Zinic stearas and 2.5ml oil amine are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 80 DEG C of about 10min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 50min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 25s at once. After having injected, then it is warming up to 290 DEG C, insulation 30min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Fig. 7 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of the core-shell nano line of the coated copper nano-wire formation of zinc oxide shell of branched frame.Fig. 8 is X-ray diffraction (XRD) figure of this product, it was demonstrated that product is the copper of face-centred cubic structure, and the zinc oxide of wurtzite structure.
Embodiment 5:
0.2mmol cupric chloride, 0.1mmol acetylacetonate nickel, 0.5mmol tri-octyl group phosphorus oxide, 6ml oil amine are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 220 DEG C, insulation 40min. In addition; 0.40g Zinic stearas and 2ml oil amine are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 80 DEG C of about 20min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 40min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 35s at once. After having injected, then it is warming up to 295 DEG C, insulation 30min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Fig. 9 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of the coated copper nickel metal core of zinc oxide shell of branched frame. Figure 10 be this product metal core can spectrogram, it was demonstrated that the metal core of this product is made up of copper and mickel, external sheath be zinc oxide.
Embodiment 6:
0.4mmol cupric chloride, 0.2mmol acetylacetonate nickel, 8ml oil amine are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 210 DEG C, insulation 30min. In addition; 0.60g Zinic stearas and 2ml oil amine are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 75 DEG C of about 15min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 30min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 20s at once. After having injected, then it is warming up to 290 DEG C, insulation 30min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Figure 11 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of the coated copper nickel metal core of zinc oxide shell of branched frame. Figure 12 be the scanning transmission line sweep of this product composite nanocrystalline can spectrogram, it was demonstrated that the metal core of this product is made up of copper and mickel, external sheath be zinc oxide.
Embodiment 7:
0.2mmol cupric chloride, 0.05mmol acetylacetonate nickel, 0.6mmol tri-octyl group phosphorus oxide, 7ml oil amine are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 200 DEG C, insulation 15min. In addition; 0.35g Zinic stearas and 2ml oil amine are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 80 DEG C of about 20min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 15min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 20s at once. After having injected, then it is warming up to 290 DEG C, insulation 45min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Figure 13 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of the coated copper nickel metal core of zinc oxide shell.
Embodiment 8:
0.2mmol acetylacetone copper, 0.01mmol acetylacetonate nickel, 1.5mmol tri-octyl group phosphorus oxide, 4ml oil amine are added in four-hole bottle, stirs under argon gas shielded, mix, be then warming up to 200 DEG C, insulation 15min.In addition; oily to 0.15g zinc acetate and 1.5ml amine and 4ml phenylcarbinol are added in there-necked flask; it is stirred under argon gas shielded and mixes; keep temperature 80 DEG C of about 25min; then this mixing solutions is drawn clean with syringe; after the reaction solution insulation 15min in four-hole bottle, being expelled in the reaction solution in four-hole bottle, whole injection process is about 40s at once. After having injected, then it is warming up to 190 DEG C, insulation 35min. Reaction solution naturally cools to room temperature, adds ethanol and product is precipitated, and by centrifugal taking-up reaction mother liquor, then uses ethanol, acetone and normal hexane mixing solutions repetitive scrubbing, then dry, obtains powder body product.
Figure 14 is the transmission electron microscope photo of this product, and product is the composite nanocrystalline of branched frame oxide coated by zinc copper nickel metal core.
Embodiment 9:
Composite nanocrystalline powder body prepared by 10mg embodiment 7 is positioned in the aqueous solution of rhodamine B that 100mL concentration is 10mg/L, darkroom is stirred 2h, to reach adsorption equilibrium. Then start to carry out photocatalytic with the ultraviolet lamp of 175W, just take out the solution after a certain amount of light-catalyzed reaction at set intervals, and calculate the ratio C/C of its absorbancy and initial absorbance0(degradation curve). The zinc oxide nanocrystalline powder body of same quality is carried out contrast test at identical conditions, records its absorption spectrum. As shown in figure 15, compared with single zinc oxide nanocrystalline, composite nanocrystalline has higher catalytic activity to photocatalysis efficiency comparing result. The composite nanocrystalline catalyzer that similar result is also prepared in other embodiment finds. Figure 16 be catalyst powder by the schematic diagram of magnet adsorption, illustrate that it has the separable feature of magnetic.
Claims (10)
1. the brilliant photocatalyst of copper nickel-zinc oxide compound nano, it is characterized in that it take cuprum nickle duplex metal as core, coating zinc oxide nanometer crystalline substance wholly or in part outside core, stable heterogeneous interface is formed by epitaxy, and forming composite nanocrystalline, described composite nanocrystalline comprises branched rack-like composite nanocrystalline, the nano wire of nucleocapsid structure, the nano particle of nucleocapsid structure, pyramid shape composite nanocrystalline.
2. the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 1, it is characterized in that described composite nanocrystalline is of a size of 20～400nm, core is of a size of 10～200nm, and the mol ratio of nickel in core can be 0～40%, and the mol ratio of nickel in core is not 0.
3. the preparation method of the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 1, it is characterised in that comprise the following steps:
1) under the protection of rare gas element, metal precursor, alkylamine or alkylamine and organic solvent mixed solution, tensio-active agent are added hybrid reaction in reaction vessel, obtains reaction solution A; Described metal precursor comprises copper metal precursor and nickel metal precursor;
2) in another container, zinc oxide precursor, alkylamine or alkylamine and organic solvent mixed solution is added; mix under the protection of rare gas element; reaction solution B is obtained after reacting by heating; reaction solution B is injected into step 1) in the reaction solution A of gained; it is warming up to 190～300 DEG C again; insulation 10～120min; then room temperature it is cooled to; product organic solvent mixed solution cleans; centrifugation again; after vacuum-drying, obtaining the brilliant photocatalyst of copper nickel-zinc oxide compound nano, the brilliant photocatalyst of gained copper nickel-zinc oxide compound nano is powder body.
4. the preparation method of the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 3, it is characterised in that in step 1) in, described copper metal precursor is selected from acetylacetonate compound or the halide salt of copper;Described nickel metal precursor is selected from the acetylacetonate compound of nickel; The molar percentage of described copper metal precursor in metal precursor can be 60%～100%; Described alkylamine can be selected from oil amine or stearylamine; Described organic solvent can be selected from dibenzyl ether or phenylcarbinol.
5. the preparation method of the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 3, it is characterised in that in step 1) in, the molar percentage of described alkylamine in alkylamine and organic solvent mixed solution is 20%～100%; Described tensio-active agent agent can be selected from cetyl alcohol, dodecane glycol, hexadecane diol, three octyl group phosphorus oxide one or both; The mol ratio of described metal precursor, alkylamine or alkylamine and organic solvent mixed solution can be 0.01～0.2; The mol ratio of described metal precursor and tensio-active agent can be 1～8; The temperature of described reaction can be 180～280 DEG C, and the time of reaction can be 10～60min.
6. the preparation method of the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 3, it is characterised in that in step 2) in, the one that described zinc oxide precursor is selected from zinc acetate, Zinic stearas; Described zinc oxide precursor and step 1) in the mol ratio of metal precursor can be 1～15; The one that described alkylamine can be selected from oil amine, cetylamine, trioctylamine; Described organic solvent can be selected from phenylcarbinol or dibenzyl ether, and described alkylamine molar percentage in alkylamine and organic solvent mixed solution can be 40%～100%.
7. the preparation method of the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 3, it is characterized in that in step 2) in, the consumption of described alkylamine or alkylamine and organic solvent mixed solution and step 1) in alkylamine or the volume ratio of alkylamine and organic solvent mixed solution consumption be 0.1～1.
8. the preparation method of the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 3, it is characterised in that in step 2) in, the temperature of described reacting by heating is 60～80 DEG C, and the time of reacting by heating is 5～30min; Described injection can adopt syringe abstraction reaction liquid B, is injected into step 1 by syringe pump or manual mode) in the reaction solution A of gained; The time of described injection can be 10～40s; 2～6 times capable of washing of described cleaning.
9. application in organic dye photocatalytic degradation agent prepared by the brilliant photocatalyst of copper nickel-zinc oxide compound nano as claimed in claim 1.
10. apply as claimed in claim 9, it is characterised in that its concrete steps are as follows:
Brilliant for copper nickel obtained by 10mg-zinc oxide compound nano photocatalyst is positioned in the aqueous solution of rhodamine B organic dye that 100mL concentration is 10mg/L, darkroom is stirred 2h, to reach adsorption equilibrium; Then start to carry out photocatalytic with the ultraviolet lamp of 175W, just take out the solution after a certain amount of light-catalyzed reaction at set intervals; When rhodamine B degraded becomes colorless completely, just stop the irradiation of ultraviolet lamp; The rhodamine B solution centrifugal of different palliating degradation degrees that will take out again, then carries out absorption spectrum test, calculate its at set intervals after the absorbancy of rhodamine B and the ratio C/C of initial absorbance0。
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